CN1651479A - Manufacturing method of biodegradable high polymer material-polylactic acid - Google Patents
Manufacturing method of biodegradable high polymer material-polylactic acid Download PDFInfo
- Publication number
- CN1651479A CN1651479A CN 200410013681 CN200410013681A CN1651479A CN 1651479 A CN1651479 A CN 1651479A CN 200410013681 CN200410013681 CN 200410013681 CN 200410013681 A CN200410013681 A CN 200410013681A CN 1651479 A CN1651479 A CN 1651479A
- Authority
- CN
- China
- Prior art keywords
- lactic acid
- poly
- heat
- catalyst
- heating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
A process for preparing biodegradable high-molecular polylactic acid features that the monometal or bimetal nano-catalyst or the combined two-element nano-catalyst is added by multiple steps, and such techniques as negative-pressure convection of heat medium, exhausting gas, microwave irradiating, and rotary heating are used for high efficiency and output rate.
Description
Technical field
The present invention relates to a kind of manufacture method of macromolecular material-poly(lactic acid) of fully biodegradable.
Background technology
Fully biodegradable plastics poly(lactic acid) is to utilize renewable resources to be raw material, through technology method synthetic such as biotechnology and chemical technologies.It is with its excellent mechanical property, wide application field, significant environmental benefit and social benefit, is attracted attention by the public and favor, and it is useful to environment, is the good material of alternative Nonrenewable resources petroleum-based plastics.Existing fully biodegradable macromolecular material poly(lactic acid) of producing, nothing more than following several synthesis technology method is arranged: a kind of is directly the dewater production technology method (also being one-step polymerization method) of polycondensation synthesizing polylactic acid of lactic acid; A kind of be lactic acid through dewatering agent, remove the moisture content in the lactic acid, and then be the production technology method of poly(lactic acid) through the protection of inert gas chemosynthesis; Also having a kind of is that lactic acid generates rac-Lactide through cyclodehydration, at the production technology method (also being the two-stage polymerization method) that becomes poly(lactic acid) by the rac-Lactide ring-opening polymerization or the like technological method, on producing, adopt above-mentioned several polymerization processs, the fully biodegradable macromolecular material poly(lactic acid) of producing, is difficult for realizing automatization, the poly(lactic acid) production yield rate is low, the used time of reactive polymeric system is long, product quality is relatively poor, cost is high, power consumption is big and environment is also had shortcoming such as pollution its technology operation more complicated.These shortcomings have been not suitable for current cleaner production, protection environment, have reduced the requirement of energy consumption and production cost etc., this also undoubtedly be to have hindered fully biodegradable macromolecular material poly(lactic acid), the application in each Application Areas.
Summary of the invention
The object of the present invention is to provide the manufacture method of the macromolecular material-poly(lactic acid) of a kind of cleaner production, efficiently synthetic fully biodegradable.
The present invention has optimized the production technique and the production technology of traditional in the past lactic acid synthesizing polylactic acid, and initiative is in lactic acid or lactic mixt ring-opening polymerization or direct condensation synthesizing polylactic acid reaction system, used the technology method of the combination of " multistep interpolation " nanometer bi-metal catalyst and nanometer single-metal reforming catalyst or " multistep interpolation " nanometer binary catalyst and other applications catalyst and used novel process and new technology such as heat-conduction medium negative pressure convection current exhaust microwave radiation rotation heating technique, made the efficient chemistry of lactic acid or lactic mixt aggregate into poly(lactic acid) into high yield.The production technique and the production technology of this lactic acid high-level efficiency chemistry synthesizing polylactic acid, have production technology simple to operate, realize that automatization, poly(lactic acid) production yield rate height, used time of reactive polymeric system are short easily, advantages such as power consumption and cost reduction greatly, superior product quality, the pollution of reactive polymeric system three-waste free discharge.These advantages have improved poly(lactic acid) beyond doubt greatly; competitive power on polymer degradable material market; make fully biodegradable macromolecular material poly(lactic acid); effectively in field of environment protection and each Application Areas; bring into play bigger effect, also reaching the efficient synthetic purpose of poly(lactic acid) cleaner production simultaneously.
Technical scheme of the present invention is: the present invention adopts two kinds of schemes, by lactic acid or lactic mixt, through optimum process technology route and the best polymerization or the synthetic reaction system technical scheme of polycondensation of chainextender chain extension and " multistep interpolation " nm-class catalyst and heat-conduction medium negative pressure convection current exhaust microwave radiation rotation heating technique direct condensation or the synthetic high yield poly(lactic acid) of ring-opening polymerization, make the poly(lactic acid) of lactic acid high-level efficiency, three-waste free discharge pollution, chemical polymerization, high yield.
Technical scheme is synthesized in the processing technology routine of scheme one (genus direct polycondensation method) lactic acid or lactic mixt polycondensation synthesizing polylactic acid and polycondensation:
1. processing technology routine:
This " scheme one " can adopt two kinds of processing technology routines, finishes lactic acid polycondensation synthesizing polylactic acid.
(1). add chainextender in the lactic acid, through routine heating or heat-conduction medium negative pressure convection current exhaust microwave radiation rotation heating lactic acid pre-expansion chain processed, after dehydration, add nanometer bi-metal catalyst in the lactic acid, through routine heating or heat-conduction medium negative pressure convection current exhaust microwave radiation rotation heating chain extension precondensation, the precondensation product adds the nanometer single-metal reforming catalyst and adds thermal polycondensation or polymerization gets poly(lactic acid) through the rotation of heat-conduction medium negative pressure convection current exhaust microwave radiation.
(2). add chainextender and nanometer combination binary catalyst in the lactic acid, through routine heating or the polycondensation of heat-conduction medium negative pressure convection current exhaust microwave radiation rotation heating lactic acid continuously dehydrating chain extension, polycondensation product adds nanometer combination binary catalyst and adds thermal polycondensation or polymerization gets poly(lactic acid) through the rotation of heat-conduction medium negative pressure convection current exhaust microwave radiation.
2. technical matters is set forth:
A. this " scheme one " related lactic raw material can be D-lactic acid, L-lactic acid and D.L-lactic acid, also can be one or both mixing raw materials of D, L, D.L one or both and other monomeric substance wherein, lactic raw material purity be that 50% technical grade-99.8% high-purity medical level all can.
B. originally " " the polymer/nanometer level catalyzer that can select for use is in the periodic table of elements to scheme one: I family, II family, III family, IV family, metal in V family and the group of the lanthanides, the combination of one or both in metal oxide and the metallic salt or two kinds is as the nanometer single-metal reforming catalyst or the nanometer bi-metal catalyst of polymerization system, as zinc, tin, titanium, lanthanum, zinc oxide, antimonous oxide, titanium dioxide, lanthanum sesquioxide, tin protochloride, stannous octoate, tin acetate, stannous octoate and zinc oxide compound, zinc oxide and antimonous oxide compound, zinc oxide and lanthanum sesquioxide compound or the like; Also have by metal carboxylate and p-methylphenyl sulfonic acid compound nanometer and make up binary catalyst: compound, the zinc lactate of stannous octoate and p-methylphenyl sulfonic acid and compound, the SnCl of p-methylphenyl sulfonic acid
22H
2O and p-methylphenyl sulfonic acid compound or the like.Available chainextender is: vulcabond, tetramethylolmethane, dicarboxylic anhydride, sorbyl alcohol, adjacent benzene tetracarboxylic acid, diepoxide class, bisoxazoline class or the like.
" catalyzer ", as the important element in lactic acid polycondensation or the polymerization reaction system, it plays process and the generation of reactant and the productive rate of reactant of forming a connecting link, quicken to promote reaction system, thereby plays important effect in reaction system.So in this " scheme one ", selected catalyzer is and has no side effect, catalytic activity is higher, and initiative has been used " nanometer single-metal reforming catalyst " and " nanometer bi-metal catalyst " and has been reached nm-class catalysts such as " nanometer combination binary catalysts " in lactic acid or lactic mixt polycondensation or polymerization polylactic acid chemical reaction system." nm-class catalyst ", in lactic acid polycondensation or polymerization reaction system, have and equal typical catalyst, higher catalytic efficiency and catalytic activity and lower residual quantity, and have the process of quickening to promote the polymerization system reaction, shorten the reaction times, the consumption that has reduced material, the production yield rate that has improved poly(lactic acid), catalyzer dissolves in many advantages such as all even system addition of polymerization system reduces, polymerization system non-pollution discharge.
Lactic acid or lactic mixt polycondensation are synthesized in the reaction system in this " scheme one ", because initiative has been used " heat-conduction medium negative pressure convection current exhaust microwave radiation rotation heating technique ", the reactions steps and the heating sequence of traditional heating reaction system have been changed, thereby also changed in the reaction system, catalyzer is concentrated the method and the operation of throwing in.In order to be fit to the needs of the synthetic reaction system of new polycondensation, through the repeatedly definite and at first proposition of experiment, in lactic acid or the synthetic reaction system of lactic mixt polycondensation, use " multistep interpolation " " nanometer bi-metal catalyst " and " nanometer single-metal reforming catalyst " and reach the input technology method of " nanometer combination binary catalyst " and add order.Thereby effectively solved in the synthetic chemical reaction system of polycondensation, reduction activity of such catalysts such as concentrated input catalyzer easily gathers, easily lumps, easily precipitates, make the synthetic chemical reaction velocity of polycondensation slack-off, it is too much that resultant of reaction contains catalyst residue, increased the cost that reactant is purified, reduced the production yield rate of reactant, many disadvantages such as product quality variation.Thereby make the poly(lactic acid) synthetic high yield of the high efficiency polycondensation of lactic acid or lactic mixt, cleaning.
Catalyzer put-on method one: be with " nm-class catalyst " conventional composite catalyst is divided into twice or repeatedly the order add in the reaction system, adding for the first time is that 3/5 of " nm-class catalyst " or conventional composite catalyst total amount added in the high-pure lactic acid prepolycondensate of process dehydration chain extension, carries out precondensation; Adding for the second time is after the lactic acid precondensation is finished, lactic acid precondensation product and remaining 2/5 " nm-class catalyst " or conventional composite catalyst are inserted together in " heat-conduction medium negative pressure convection current exhaust microwave radiation rotation heating " device, through carry out microwave radiation heating polycondensation synthesizing polylactic acid.This multistep adds that " technology method of " nm-class catalyst " or conventional catalyst; can effectively improve the efficient of catalyzer; can keep catalyzer to have higher activity again; to shorten polycondensation reaction time effectively raises production yield rate and the quality of product and higher many advantages such as molecular weight of poly(lactic acid).
Catalyzer put-on method two: be that " nm-class catalyst " or conventional catalyst are sequentially added in the reaction system, adding for the first time is that " nm-class catalyst " or conventional composite catalyst are added in the high-pure lactic acid prepolycondensate of process dehydration chain extension, carries out precondensation; Adding for the second time is after the lactic acid precondensation is finished, lactic acid precondensation product and " nm-class catalyst " or conventional catalyst are inserted together in " heat-conduction medium negative pressure convection current exhaust microwave radiation rotation heating " device, aggregate into poly(lactic acid) through carry out microwave radiation heating.This method is: dewatering and the catalyzed polymerization performance of having utilized both sexes " nm-class catalysts ", make the dehydration chain extension lactic acid precondensation of further dewatering become high-molecular weight polymer, and obtain high yield by polymkeric substance, high-performance, high molecular weight polylactic acid.
In above-described two kinds of methods, catalyzer and interpolation order by changing different components can be combined into many methods, have not just enumerated one by one here.
Poly(lactic acid) is the macromolecular compound that development in recent years is easily degraded rapidly, the present invention can together add metal ion purifying agent MD1024 with catalyzer in lactic acid or lactic mixt polycondensation or polymerization process, (consumption catalyzer: purifying agent=1: the poly(lactic acid) aging resistance that 0.5-2) prepares is remarkable.
For thermostability and mechanical property and the relative molecular weight that improves poly(lactic acid), this " method one " adopted chainextender to carry out the method for the chain extension of lactic acid polycondensation low molecular weight, and the performance of poly(lactic acid) is improved greatly.Use chainextender: have (1) active terminal hydroxy group in the poly(lactic acid) is sealed, improved the thermostability of product; (2) introduce functional group by chainextender, the mechanical property of poly(lactic acid) and manufacturing property are improved; (3) the chainextender consumption is few, does not have advantages such as the separation of being permitted.
C. heat-conduction medium negative pressure convection current exhaust microwave radiation is rotated heating technique
C.1 technology is set forth
Microwave energy field promotes organic chemistry system building-up reactions technology, is the front subject that develops rapidly at present.The eighties in 20th century, microwave began to obtain extensive studies and utilization in chemical field, and had obtained positive progress and fruitful effect in organic chemistry building-up reactions system, and this can be described as the field technology revolution in the chemical field.Microwave is meant that wavelength is 1mm-1m, and range of frequency is 300-300,000MHz, and the hertzian wave with penetrance, industrial employed microwave frequency is 915MHz and two frequencies of 2450MHz.Microwave is in the organic chemistry building-up reactions, have unique effect and advantage, it have be rapidly heated, body heating, fast reaction speed, shortening reaction times, reduce side reaction, improve reaction preference and productive rate, saving energy consumption, advantage such as free from environmental pollution.
At present, academia it is generally acknowledged that microwave comes from its heat effect to polar material to the high efficiency of organic chemistry building-up reactions both at home and abroad.After polar molecule is accepted microwave radiation energy, produce internal heat effect by molecular dipole high speed rotating and vibration (per second several hundred million times to tens polarization), microwave is extremely tangible to the heat effect of polar molecule, and with traditional type of heating be distinct by thermal conduction and thermal convection process.The specific inductivity of polar molecule is bigger, with microwave stronger coupling is arranged, and non-polar molecule does not produce or produce more weak coupling with microwave.In common material, ferromagnetic metal and metallic conductor are used for the shield microwaves radiation because of absorption and microwave reflection.Glass, pottery etc. can see through microwave, itself produces heat effect hardly, thereby can be used to make the material of reactor, most of organic compound and hydrous matter, polarity inorganic salts etc. can well absorb microwave, these performances and characteristics are microwave irradiation technology, can enter the synthetic field of organic chemistry smoothly and establish solid basis.
The microwave technology success be applied to the organic chemistry building-up reactions, make traditional organic chemistry synthesising reacting speed improve several times, hundreds of times even thousands of times.But microwave technology is applied in the lactic acid organic synthesis poly(lactic acid) reaction system, also only is a starting stage.Bibliographical information is arranged; blanketing with inert gas rac-Lactide microwave heating chemical polymerization becomes the report of poly(lactic acid); but to the technical suitability for industrialized production that do not reach of this item up to now; still in laboratory stage; reason be this technology in polymerization reaction system, decompression operation is difficulty relatively, it is also very inconvenient to charge into shielding gas; cost is higher or the like, and can't reach industrial requirement.
Lactic acid oligomer and polymerization single polymerization monomer rac-Lactide, belong to nonpolar xln, absorb relatively poor to microwave radiation energy, directly the applied microwave quantity of radiant energy is carried out heated polymerizable, its effect is not very good, can cause on the contrary that polymerization system heating is uneven, polymerization time is long, power consumption is big, loss of material is too much, polymerisate quality variation, polymer molecular weight be low or the like, and many disadvantages of bringing.In order to solve lactic acid and lactic acid oligomer and polymerization single polymerization monomer rac-Lactide, be not suitable for problems such as applied microwave radiation direct polymerization or polycondensation heating and acid by dehydrating lactic steam distribute, through thinking deeply in many ways and consulting a large amount of pertinent datas and through repeatedly research decision, utilize the strong material by microwave application that absorbs to excite and principles such as the principle of heat production and convection of air exhaust through microwave radiation, the moisture content of discharging the acid by dehydrating lactic system for lactic acid oligomer and polymerization single polymerization monomer rac-Lactide indirect heating and forced air convection, this " heat-conduction medium negative pressure convection current exhaust microwave radiation rotation heating " just of the present invention technology.
C.2 " heat-conduction medium negative pressure convection current exhaust microwave radiation rotation indirect heating " principle
Many organic reactants can not directly absorb micro-wave energy (as: organism such as lactic acid oligomer and polymerization single polymerization monomer rac-Lactide) significantly, but the microwave field energy is radiated on the surface of containing certain " the high material by microwave application that absorbs ", because the strong effect of " the high material by microwave application that absorbs " surface and interior molecules and microwave field energy, micro-wave energy will be by transition heat, thereby make " the high material by microwave application that absorbs " be heated to very high temperature very soon.Although the reaction mass in the reactor can be by the micro-wave energy direct heating, but when reaction mass through reactor and " high absorb material by microwave application " that be subjected to microwave-excitation when contacting, " the high material by microwave application that absorbs " passes to the heat of self in the reaction mass by reactor, the temperature that makes reaction mass raises rapidly and reaches the temperature of required self-polymerization, thereby has finished the process of " heat-conduction medium microwave radiation indirect heating ".
Heat-conduction medium negative pressure convection current exhaust microwave heating acid by dehydrating lactic system: be to utilize microwave inside heating characteristics and vacuum fan to form the negative pressure convection current, make the inside and outside steam moisture content that dewaters in the pressure gradient discharge lactic acid that produces of filter cake reach the purpose of quickening acid by dehydrating lactic.The exhausting system of dehydration equipment can be walked moisture content by convective zone on the one hand, makes dewatering system form negative pressure on the other hand and prevents lactic acid at high temperature, the dissipation of the sour gas of generation.
C.3 " heat-conduction medium " chooses
The material that absorbs microwave as heat-conduction medium by force is a lot, and ferromagnetic material is arranged, the metal oxide of valence variation element, materials such as fibrous substance and carbide.Ferromagnetic material has very strong microwave absorption capacity, and strong absorption microwave in microwave field and being heated has characteristics such as heat-up rate is fast, good heat-transfer.But ferromagnetic material is surpassing more than 100 ℃ factor such as bulk absorption microwave deterioration of efficiency, unstable properties not competent " heat-conduction medium " as this technology; The metal oxide of valence variation element easily decomposes in strong microwave field, also is not suitable as " heat-conduction medium "; Carbide is good microwave absorbing material.In carbide family, activated carbon has very strong microwave absorbing property, but as " heat-conduction medium ", it adds to pine for producing at microwave field cremates, and temperature raises too fast, and temperature is very high-leveled and difficult with control, also is not suitable as " heat-conduction medium "; Silicon carbide (Sic) is a kind of strong absorption material by microwave application, in microwave field, absorb microwave and be heated, and it is fast to have heat-up rate, good heat-transfer, and in certain temperature range, can keep stable performance, and thermal runaway phenomenon can not appear, can use repeatedly, as one of this technology the best " heat-conduction medium " preferred material.So the present invention selects for use silicon carbide conduct " heat-conduction medium " or dissipation material as heat-conduction medium.
C.4 the using method of " heat-conduction medium "
" heat-conduction medium " silicon carbide (Sic) generally has the using method of three kinds of indirect heat transfers in lactic acid organic chemistry synthetic system:
First method: with silicon-carbide particle or powder; directly uniformly place mat is in microwave heater on ceramic pallet or the glass of anti-burning pallet; be placed on the pallet that is covered with silicon carbide at the reactor that will fill lactic acid oligomer or polymerization single polymerization monomer rac-Lactide; carry out carry out microwave radiation heating; at this moment silicon carbide is at first by microwave heating; the silicon carbide that has been heated; bottom by reactor passes to heat in polycondensation or syndicated feeds material lactic acid oligomer or the polymerization single polymerization monomer rac-Lactide uniformly; at this moment polycondensation or syndicated feeds material lactic acid oligomer or polymerization single polymerization monomer rac-Lactide have compiled two next heats of approach, and (one is the heat from the silicon carbide conduction; one is the heat that produces from the microwave direct radiation) heating simultaneously; carry out polycondensation or aggregate into poly(lactic acid), thus finished " heat-conduction medium carry out microwave radiation heating " cross into.This method is simple and practical, and by regulating silicon carbide laying amount or regulating microwave power, can obtain different equilibrium temperatures.
Second method: with silicon-carbide particle or powder and TTZF type high-temperature adhesives (the also high-temperature adhesives of available other type); ratio in 3 to 1 mixes; spread upon the glass reactor of anti-burning the or following reactor outside, ceramic reactor efficient loading position and bottom then uniformly; smearing thickness examination reactor size and reactive polymeric are temperature required and decide (common laboratory reaction unit be coated with about 0.1mm-5mm thickness both can); smear evenly and solidify after drying is finished after a while; smearing TTZF type high-temperature adhesives with high-temperature fibre; bundle is bonded at the silicon carbide of smearing last time, and (this operation is to prevent that silicon carbide from high temperature coming off; influence the thermo-efficiency of polymerization system); after treating the tackiness agent drying; water or other solvent that it is suitable that reactor is packed into are put into microwave heating installation; slowly improve microwave power and heat 30min to 1000W; after heating is finished; take out reactor after cooling, smear again promptly can heat after one deck TTZF type tackiness agent drying and used.Heat-processed and first method are basic identical.This method indirect heating and homogeneity are better than first method, and this making method simple, be easy to make, regulate microwave output power and can obtain different equilibrium temperatures.Present method and heat-processed have acid by dehydrating lactic, precondensation, polycondensation or polymerization appearance and are the effect of one, use than complication experiment chamber and chemical engineering industry cleaner production.
The third method: when making microwave field radio polymerization reactor; with silicon carbide powder or powder; ratio via 3 to 1 mixes the back with TTZF type tackiness agent, and (this operation mainly is that the heat conduction interlayer is closely linked to each other with the reactor inside and outside wall; muddy is one, has more shock-resistance and thermal conduction.This operation also can, tackiness agent also can use the high-temperature adhesives and the heat-conduction medium of other type), embed below effective loading of the glass reactor of anti-burning of manufacturing or ceramic reactor, between reactor outside and the bottom ectonexine, constitute silicon carbide thermal conduction reactor heat-conduction medium intermediate course.Heat-conduction medium thickness of interlayer examination reactor size and reactive polymeric are temperature required and decide, and produced in this way reactor and thermal conduction system are muddy to be one, has more its practicality and standard.This method has the heat conduction efficiency height, homogeneous heating, and reactor is simple to operate, cleaning is fit to standardized production, has more that the raw material dehydration concentrates, incorporate effects such as polycondensation or polymerization, regulate microwave output power and can obtain different equilibrium temperatures, microwave heating and preceding two examples are basic identical.This integrated reactor just is being fit to the service requirements of current cleaner production.
3. the method for two kinds of processing technology routine direct condensation of lactic acid synthesizing polylactic acid
The explanation of first kind of lactic acid polycondensation synthesizing polylactic acid processing technology routine
Method one:
Acid by dehydrating lactic is handled:
Acid by dehydrating lactic is handled and can be adopted conventional heating decompression or normal pressure dewatering process, promptly controls under the condition of appropriate vacuum and temperature and chainextender, reduces pressure or normal pressure is removed moisture content in the lactic acid, and the acid by dehydrating lactic oligopolymer is carried out pre-chain extension.Conventional heating temperature for removing water is 80-120 ℃, and vacuum tightness is 10-110mmHg, and dewatering time is 120min.If in routine heating decompression or normal pressure processed process, use the auxiliary material that stirs of agitator, can improve the efficient that dewaters.
Precondensation:
With dehydration chain extension lactic acid oligomer is raw material, under the catalysis of routine heating and both sexes " nm-class catalyst ", reduces pressure or normal pressure chain extension lactic acid oligomer dehydration precondensation.The precondensation temperature is 90-160 ℃, adopts in the polycondensation process slowly to rise to the pyritous method from low temperature, to prevent in the polycondensation process that the lactic acid oligomer material loss too much and prevent the carbonization of precondensation product.Precondensation vacuum tightness 10-110mmHg, the precondensation time is 300min.
Condensation polymerization:
In the presence of " nm-class catalyst ", be raw material " heat-conduction medium negative pressure convection current exhaust microwave radiation rotation heating " normal pressure polycondensation with the lactic acid prepolycondensate, the polycondensation microwave power is 50-500W, the polycondensation time is 10-28min.
Embodiment one
With 150g purity be 85% L-lactic acid and chainextender 0.1-0.26g vulcabond together, join in the 500ml three-necked flask that has agitator, stir post-heating, system temperature reaches 100 ℃ to begin to vacuumize, and in vacuum tightness is to stir the pre-chain extension 120min of dehydration under the condition of 60-100mmHg.After dehydration is finished, reaction system slowly is warmed up to 140 ℃ from 100 ℃, the nanometer bi-metal catalyst that adds 0.3-0.6g both sexes " Nano-class zinc oxide and lanthanum sesquioxide " composition (is pressed mass ratio 1: 0.06--0.2, catalyst levels and monomeric mass ratio are 1: under catalysis 100-4000) and the vacuum tightness 40-80mmHg condition, continue dehydration chain extension precondensation 210-300min.After precondensation is finished, the precondensation product is taken out, pack into outer and the bottom is coated with in the beaker of " heat-conduction medium " coat of silicon carbide, after adding 0.06-1g " nano level stannous octoate " catalyzer again, put into microwave oven with the good beaker mouth of diaphragm seal, regulating microwave output power is under the condition of 50-500W, carries out polycondensation 10-28min, promptly gets transparent substance poly(lactic acid) (PLA).
Embodiment two
Being 85% D.L-lactic acid and 0.3-1.6g " Nano-class zinc oxide " and 0.1-0.26g vulcabond with 150g purity (presses mass ratio 1: 0.2-1) Zu He two chainextenders with tetramethylolmethane, join in the 500ml three-necked flask that has agitator, stir post-heating, temperature of reaction system begins to vacuumize when reaching 100 ℃, in vacuum tightness is to stir the pre-chain extension 120min of dehydration under the condition of 60-100mmHg.After dehydration is finished, system slowly is warmed up to 140 ℃ from 100 ℃, the nanometer bi-metal catalyst that adds 0.2-0.8g both sexes " Nano-class zinc oxide and antimonous oxide " composition (is pressed mass ratio 1: 0.06-0.30, catalyst levels and monomeric mass ratio are 1: catalysis 100-4000) and vacuum tightness are under the condition of 40-80mmHg, continue dehydration chain extension precondensation 210-300min.After precondensation is finished, the precondensation product is taken out, pack into outer and the bottom is coated with in the beaker of " heat-conduction medium " coat of silicon carbide, after adding 0.06-1g " nano level stannous octoate " catalyzer again, put into microwave oven with the good beaker mouth of diaphragm seal, regulating microwave output power is under the condition of 50-500, carries out polycondensation 10-28min, promptly gets transparent substance poly(lactic acid) (PLA).
Two examples in the above method one can just can be combined into the condensation polymerization architectonical of many forms by changing " nm-class catalyst " and adding order, have not just exemplified one by one here.
Method two:
Acid by dehydrating lactic is handled:
Acid by dehydrating lactic is handled and can be adopted " heat-conduction medium negative pressure convection current exhaust microwave radiation rotation heating " normal pressure or " heat-conduction medium carry out microwave radiation heating " vaccum dewatering technology, promptly control under the condition of the output rating of suitable " heat-conduction medium negative pressure convection current exhaust microwave radiation rotation heating " and dehydration catalyst and chainextender, carry out normal pressure or vacuum and remove moisture content in the lactic acid, and the acid by dehydrating lactic oligopolymer is carried out pre-chain extension, removing water-horse power is 50W-1000W, and dewatering time is 20-100min.
Precondensation:
With dehydration chain extension lactic acid oligomer is raw material, under the catalysis of " heat-conduction medium negative pressure convection current exhaust microwave radiation rotation heating " and both sexes " nm-class catalyst ", carry out normal pressure or vacuum chain extension lactic acid oligomer and continue the dehydration precondensation, precondensation power is 50-520W, adopt the method that slowly rises to superpower output from low power output in the polycondensation process, to prevent in the polycondensation process lactic acid oligomer material loss too much and prevent the carbonization of precondensation product, the precondensation time is 28-110min.
Condensation polymerization:
In the presence of " nm-class catalyst ", be raw material " heat transfer medium negative pressure convection current exhaust microwave radiation rotation heating " normal pressure polycondensation with the lactic acid prepolycondensate, the polycondensation microwave output power is 50-500W, the polycondensation time is 10-28min.
Embodiment one
With 150g purity be 85% L-lactic acid and 0.1--0.26g vulcabond together, join the outer and bottom of 500ml and be coated with in the beaker of " heat-conduction medium " coat of silicon carbide.After stirring, put into the microwave radiation rotary funace that has negative pressure convection current exhaust system, microwave output power is slowly regulated being increased under the 50-450W the pre-chain extension 20-100min of thermal dehydration.After the pre-chain extension of acid by dehydrating lactic is finished, the slow adjusting of microwave output power is increased to 50-480W, under the catalysis of the nanometer bi-metal catalyst that adding 0.3-0.6g both sexes " Nano-class zinc oxide and lanthanum sesquioxide " are formed, continue dehydration chain extension precondensation 28-110min.After precondensation is finished, behind adding 0.06--1g " nano level stannous octoate " catalyzer, put back in the microwave oven with the good beaker mouth of diaphragm seal, the adjusting microwave output power is 50-500W, and polycondensation 10-28min promptly gets transparent substance poly(lactic acid) (PLA).
Embodiment two
Being 85% D.L-lactic acid and 0.3-1.6g " Nano-class zinc oxide " and 0.1-0.26g vulcabond with 150g purity, (press mass ratio 1: 0.2-1) Zu He two chainextenders join the outer and bottom of 500ml and are coated with in the beaker of " heat-conduction medium " coat of silicon carbide with tetramethylolmethane.After stirring, put into the microwave radiation rotary funace that has negative pressure convection current exhaust system, microwave output power is slowly regulated being increased under the 50-450W the pre-chain extension 20-100min of thermal dehydration.After the pre-chain extension of acid by dehydrating lactic is finished, the slow adjusting of microwave output power is increased to 50-480W, under the catalysis of the double-metal composite catalyst that adding 0.2-0.8g both sexes " Nano-class zinc oxide and antimonous oxide " are formed, continue dehydration chain extension precondensation 28-110min.After precondensation is finished, behind adding 0.06-1g " nano level stannous octoate " catalyzer, put back in the microwave oven with the good beaker mouth of diaphragm seal, the adjusting microwave output power is 50-500W, and polycondensation 10-28min promptly gets transparent substance poly(lactic acid) (PLA).
Two examples in the above method two can just can be combined into the condensation polymerization architectonical of many forms by changing " nano level compound catalyst " and adding order, have not just exemplified one by one here.
The explanation of second kind of lactic acid polycondensation synthesizing polylactic acid processing technology routine
Method one:
Present method one be by lactic acid in the presence of chainextender and " nanometer combination binary catalyst ", through two kinds of thermals source (conventional heating and heat-conduction medium negative pressure convection current exhaust microwave radiation rotation heating) heating, the method of dividing " multistep interpolation " " nanometer combination binary catalyst ", under decompression and the normal pressure, is 50-500W in 100-190 ℃ with output rating, vacuum tightness is under 10-100mmHg and the non-pressurized condition, dehydration polycondensation 540min, get the poly(lactic acid) crude product, crude product gets purified poly(lactic acid) after refining drying.
Embodiment one
With 150g purity is that the vulcabond of 85% L-lactic acid and 0.1-0.26g and " the nano level stannous octoate is with p-methyl benzenesulfonic acid " of 0.12-0.4g (are pressed mass ratio 1: 0.1-1.6) combination binary catalyst, join in the 500ml three-necked flask that has agitator, after stirring, heating slowly is warming up to 100-190 ℃, vacuum tightness is under the condition of 50-100mmHg, dehydration chain extension polycondensation 300-480min.After the dehydration polycondensation is finished, polycondensation product is taken out, pack into outer and the bottom is coated with in the beaker of " heat-conduction medium " coat of silicon carbide, after adding 0.08--0.3g " nano level stannous octoate and p-methyl benzenesulfonic acid " combination binary catalyst again, put into microwave oven with the good beaker mouth of diaphragm seal, at microwave output power is under the condition of 50-500W, continues polycondensation 10-30min, promptly gets transparent substance poly(lactic acid) (PLA).
Embodiment two
Be that (press mass ratio 1: 0.2-1) Zu He two chainextenders and 0.48-1.2g " nano level zinc lactate and p-methyl benzenesulfonic acid " (press mass ratio 1: 0.1-2) Zu He binary catalyst with tetramethylolmethane for the vulcabond of 85% D.L-lactic acid and 0.1-0.3g with 150g purity, join in the 500ml three-necked flask that has agitator, after stirring, heating slowly is warming up to 100-190 ℃, vacuum tightness is under the condition of 50--100mmHg, dehydration chain extension polycondensation 300-480min.After the dehydration polycondensation is finished, polycondensation product is taken out, pack into outer and bottom coating has in the beaker of " heat-conduction medium " coat of silicon carbide, after reaching 0.32--0.8g " nano level zinc lactate and p-methyl benzenesulfonic acid " combination binary catalyst again, put into microwave oven with the good beaker mouth of diaphragm seal, at microwave output power is under the condition of 50-500W, continues polycondensation 10-30min, promptly gets transparent substance poly(lactic acid) (PLA).
Method two
Be by lactic acid in the presence of chainextender and " nanometer combination binary catalyst ", method through " heat-conduction medium negative pressure convection current exhaust microwave radiation rotation heating " branch " multistep interpolation " " nanometer combination binary catalyst ", under normal pressure, in microwave output power is 50-500W, condition under, dehydration polycondensation 30-120min, add again by " nano level combination binary catalyst ", in microwave output power is 50-750W, continue polycondensation 10-30min, get the poly(lactic acid) crude product, crude product gets purified poly(lactic acid) after refining drying.
Embodiment one
With 150g purity is that (press mass ratio 1: 0.1-1.6) combination binary catalyst adds outer and the bottom is coated with in the beaker of " heat-conduction medium " coat of silicon carbide for the vulcabond of 85% L-lactic acid and 0.1-0.26g and " the nano level stannous octoate is with p-methyl benzenesulfonic acid " of 0.12-0.4g.After stirring, put into the microwave radiation rotary funace that has negative pressure convection current exhaust system, microwave output power is slowly regulated being increased to 50-500W, under condition of normal pressure, dehydration chain extension polycondensation 60-120min.After the dehydration polycondensation is finished, after adding " nano level stannous octoate with to methylsulphonic acid " combination catalyst of 0.08-0.3g again, putting back in the microwave oven with the good beaker mouth of diaphragm seal, is 50-550W at microwave output power, continue polycondensation 10-30min, promptly get transparency material poly(lactic acid) (PLA).
Embodiment two
Be that (press mass ratio 1: 0.2-1) (press mass ratio 1: 0.1-2) Zu He binary catalyst adds outer and the bottom is coated with in the beaker of heat-conduction medium coat of silicon carbide for the nano level zinc lactate of Zu He two chainextenders and 0.48-1.2g and p-methyl benzenesulfonic acid with tetramethylolmethane for the vulcabond of 85% D.L-lactic acid and 0.1-0.3g with 150g purity.After stirring, put into the microwave radiation rotary funace that has negative pressure convection current exhaust system, microwave output power is slowly regulated being increased to 50-500W, under condition of normal pressure, dehydration chain extension polycondensation 60-120min.After the dehydration polycondensation is finished, after adding the binary catalyst of the nano level zinc lactate of 0.32-0.8g and p-methyl benzenesulfonic acid combination again, putting back in the microwave oven with the good beaker mouth of diaphragm seal, is 50-550W at microwave output power, continue polycondensation 10-30min, promptly get transparent substance poly(lactic acid) (PLA).
Scheme two (genus two-stage polymerization) lactic acid or lactic mixt aggregate into the processing technology routine and the polymerization technique scheme of poly(lactic acid);
1. processing technology routine:
This " scheme two " can adopt two kinds of processing technology routines, finishes lactic acid polymerizes and becomes poly(lactic acid).
Add chainextender and nanometer single-metal reforming catalyst in the lactic acid, become oligopolymer through routine heating decompression or the polycondensation of heat-conduction medium negative pressure convection current exhaust microwave radiation rotation heating normal pressure dehydration chain extension, oligopolymer add nanometer bi-metal catalyst through routine heating decompression or the cracking of heat-conduction medium negative pressure convection current exhaust microwave radiation rotation heating constant-pressure and high-temperature distill crude lactide, crude lactide gets rac-Lactide from crystallization purifying, and rac-Lactide adds the nanometer single-metal reforming catalyst and makes poly(lactic acid) through heat-conduction medium microwave radiation rotation heating polymerization under atmospheric pressure.
2. Technology is set forth
The type of this " scheme two " lactic acid, the mixture of lactic acid and purity are identical with " scheme one ".
This " scheme two " available nm-class catalyst and general catalyzer are basic identical with " scheme one ".
The method of " multistep interpolation " " nm-class catalyst " that this " scheme two " used and general catalyzer is basic identical with " scheme one ".
The technology method of " heat-conduction medium negative pressure convection current exhaust microwave radiation rotation heating " that this " scheme two " used is basic identical with " scheme one ".
3. two kinds of processing technology routines of lactic acid aggregate into the method explanation of poly(lactic acid)
Method one:
The acid by dehydrating lactic polycondensation:
The acid by dehydrating lactic polycondensation can be adopted conventional heating decompression or the normal pressure polycondensating process that dewaters, promptly control under the condition of appropriate vacuum and temperature and chainextender, both sexes " nm-class catalyst ", reduce pressure or normal pressure is removed moisture content in the lactic acid, and the lactic acid polycondensate is carried out pre-chain extension.It is 80-120 ℃ that routine heats the condensation temperature that dewaters, and vacuum tightness is 10-110mmHg, dehydration polycondensation 120min.If in routine heating decompression or normal pressure dehydration polycondensation process, use the auxiliary material that stirs of agitator, can improve the polycondensation efficient that dewaters.
Pintsch process:
With chain extension lactic acid polycondensate is the source material, under the catalysis of routine heating and both sexes nano level composite catalyst, reduce pressure or normal pressure chain extension lactic acid polycondensate dehydration distillation cracking, dehydration distillation cracking temperature is 90-250 ℃, dehydration distillation cracking process adopts and slowly rises to the pyritous method from low temperature, preventing in the material dewatering distillation cracking process, material loss too much and prevent the material carbonization.Dehydration distillation cracking vacuum tightness is 10-110mmHg, and the cracking time is 30-100min, and the split product crude lactide through distilled water wash several times, again through suction filtration, ethyl acetate crystallization and purification, drying, gets pure rac-Lactide.
Polymerization:
In the presence of nm-class catalyst, be raw material heat-conduction medium microwave radiation rotation heating with the rac-Lactide, polymerization under normal pressure, the polymerization microwave output power is 50-500W, polymerization time is 10--28min.
Embodiment one
With 150g purity be 85% L-lactic acid and 0.6-1.3g both sexes Nano-class zinc oxide catalyzer together, join in the 500ml three-necked flask that has agitator and vacuum distillation apparatus, after stirring, heating, when reaching 100 ℃, system temperature begins to vacuumize, in vacuum tightness is under the condition of 60-100mmHg, stir dehydration polycondensation 120min, after the dehydration polycondensation is finished, reaction system slowly is warming up to 140 ℃ from 100 ℃, (by mass ratio 1: catalysis 0.06-0.2) and vacuum tightness are under the condition of 30-90mmHg to add the Nano-class zinc oxide of 0.3-0.6g and the bimetallic catalyst of lanthanum sesquioxide composition, the distillation of dewatering distills out the moisture content in the reaction system as far as possible, when observing when not had moisture content to be distilled out, temperature of reaction system is increased to more than 180 ℃, increase vacuum tightness, carry out scission reaction 30-90min, when temperature of reaction system reaches 255 ℃, reaction finishes, and promptly gets rac-Lactide.With the rinsing of rac-Lactide process, pumping rate, the ethyl acetate crystallization and purification, after the drying, pack into outer and the bottom is coated with in the beaker of heat-conduction medium coat of silicon carbide, add the nano level stannous octoate catalyst of 0.06-1g again after, put into the microwave radiation rotary funace with the good beaker mouth of diaphragm seal, regulating microwave output power is under the condition of 50-500W, carries out polymerization 10-28min, promptly gets transparent substance poly(lactic acid) (PLA).
Embodiment two
With 150g purity be the vulcabond of 85% D.L-lactic acid and 0.1-0.26g and 0.6-1.3g Nano-class zinc oxide together, join in the 500ml three-necked flask that has agitator and vacuum distillation apparatus, after stirring, heating, when reaching 100 ℃, system temperature begins to vacuumize, in vacuum tightness is under the condition of 60-100mmHg, stir dehydration polycondensation 120min, after the dehydration polycondensation is finished, reaction system slowly is warming up to 140 ℃ from 100 ℃, (by mass ratio 1: catalysis 0.06-0.3) and vacuum tightness are under the condition of 30-90mmHg to add the both sexes Nano-class zinc oxide of 0.2-0.8g and the bimetallic catalyst of antimonous oxide composition, the distillation of dewatering distills out the moisture content of reaction system as far as possible.When observation has not had moisture content to be distilled out, reaction system is increased to more than 180 ℃, increase vacuum tightness, carry out scission reaction 30-90min, when temperature of reaction system reached 255 ℃, reaction finished, and promptly gets rac-Lactide.With the rinsing of rac-Lactide process, suction filtration, the ethyl acetate crystallization and purification, after the drying, pack into skin and bottom are coated with in the beaker of thermal conduction Jie coat of silicon carbide, add the nano level stannous octoate of 0.06-1g again " behind the catalyzer; put into the microwave radiation rotary funace with the good beaker mouth of diaphragm seal; regulating microwave output power is under the condition of 50-500W, carries out polymerization 10-28min, promptly gets transparent substance poly(lactic acid) (PLA).
Method two:
The acid by dehydrating lactic polycondensation:
The acid by dehydrating lactic polycondensation can be adopted heat-conduction medium negative pressure convection current exhaust microwave radiation rotation heating normal pressure dehydration polycondensating process, promptly control under the condition of suitable microwave output power and chainextender and both sexes nm-class catalyst, carry out normal pressure and remove moisture content in the lactic acid, and the acid by dehydrating lactic polycondensate is carried out pre-chain extension.It is 50-500W that the polycondensation output rating that dewaters is heated in the rotation of heat-conduction medium negative pressure convection current exhaust microwave radiation, dehydration polycondensation 30-120min.
Pyrogenic distillation:
With chain extension lactic acid polycondensate is raw material, under the catalysis of heat-conduction medium negative pressure convection current exhaust microwave radiation rotation heating and both sexes nano level composite catalyst, carry out normal pressure chain extension lactic acid polycondensate dehydration distillation cracking, dehydration distillation cracking microwave output power is 50-750W, dehydration distillation cracking process adopts the method that slowly is adjusted to superpower output from low power output, preventing in the material dewatering distillation cracking process, material loss too much and prevent the material carbonization.Dehydration distillation cracking 20-90min, the split product crude lactide, through distilled water wash several times, and suction filtration, the ethyl acetate crystallization and purification, drying gets pure rac-Lactide.
Polymerization:
In the presence of nm-class catalyst, be raw material with the rac-Lactide, heat-conduction medium negative pressure convection current exhaust microwave radiation rotation heating, polymerization under atmospheric pressure, polymerization microwave output power are 50-500W, polymerization time is 10-28min.
Embodiment one
With 150g purity be 85% L-lactic acid and 0.6-1.3g both sexes Nano-class zinc oxide catalyzer together, adding skin and bottom is coated with in the beaker of heat-conduction medium coat of silicon carbide, after stirring, put into the microwave radiation rotary funace that has negative pressure convection current exhaust system, the slow adjusting of output rating of microwave oven is increased under the 50-450W, heating, normal pressure dehydration polycondensation 20-100min.After the dehydration polycondensation is finished, the output rating of microwave oven is regulated when being increased to 50-480W, add the Nano-class zinc oxide of 0.3-0.6g and the bimetallic catalyst of lanthanum sesquioxide composition and (press mass ratio 1: under catalysis 0.06-0.2), the distillation of dewatering, distill out the moisture content in the reaction system as far as possible, when observation has not had moisture content to be distilled out from sight glass, again the output rating of microwave oven is slowly regulated and be increased to 50-620W, carry out scission reaction 20-90min, promptly get rac-Lactide.With rac-Lactide through rinsing several times, suction filtration, ethyl acetate crystallization and purification, drying after, pack into outer and the bottom is coated with in the beaker of heat-conduction medium coat of silicon carbide, behind the nano level stannous octoate catalyst that adds 0.06-1g, with the good beaker mouth of diaphragm seal, put into the microwave radiation rotary funace, regulating microwave output power is under the condition of 50-500W, carries out polymerization 10-28min, promptly gets transparent substance poly(lactic acid) (PLA).
Embodiment two
With 150g purity be the vulcabond of 85% D.L-lactic acid and 0.1-0.26g and 0.6-1.3g the Nano-class zinc oxide catalyzer together, adding skin and bottom is coated with in the beaker of heat-conduction medium coat of silicon carbide, after stirring, put into the microwave radiation rotary funace that has negative pressure convection current exhaust system, the slow adjusting of output rating of microwave oven is increased under the 50-450W, heating, the pre-chain extension 20-100min of normal pressure dehydration polycondensation.After the dehydration polycondensation is finished, the output rating of carry out microwave radiation heating stove is regulated when being increased to 50-480W, add the both sexes Nano-class zinc oxide of 0.2-0.8g and the bimetallic catalyst of antimonous oxide composition and (press mass ratio 1: under catalysis 0.06-0.3), the chain extension that dewaters distillation, distill out the moisture content in the reaction system as far as possible, when observation has not had moisture content to be distilled out from sight glass, again the output rating of microwave oven is slowly regulated and be increased to 50-620W, carry out scission reaction 20-60min, promptly get rac-Lactide.
With rac-Lactide through rinsing several times, suction filtration, ethyl acetate crystallization and purification, drying after, pack into outer and the bottom is coated with in the beaker of heat-conduction medium coat of silicon carbide.Adding 0.06-1g's again " behind the nano level stannous octoate catalyst; with the good beaker mouth of diaphragm seal, put into the microwave radiation rotary funace, is under the condition of 50-500W regulating microwave output power; carry out polymerization 10-28min, promptly get transparent substance poly(lactic acid) (PLA).
Claims (10)
1, a kind of manufacture method of biodegradated polymer materal-poly(lactic acid), it is characterized in that: with lactic acid or lactic mixt is raw material, through chainextender chain extension and " multistep interpolations " nm-class catalyst with direct condensation is heated in the rotation of heat-conduction medium negative pressure convection current exhaust microwave radiation or poly(lactic acid) is made in ring-opening polymerization.
2, the manufacture method of biodegradated polymer materal-poly(lactic acid) according to claim 1, it is characterized in that described nm-class catalyst comprises: by the combination of one or both or two kinds in metal, metal oxide and the metallic salt in the I family in the periodic table of elements, II family, III family, IV family, V family and the group of the lanthanides or nanometer single-metal reforming catalyst or nanometer bi-metal catalyst, or the nanometer combination binary catalyst of forming by metal carboxylate and p-methylphenyl sulfonic acid.
3, the manufacture method of biodegradated polymer materal-poly(lactic acid) according to claim 1 and 2, it is characterized in that described direct condensation: add chainextender in the lactic acid, through routine heating or heat-conduction medium negative pressure convection current exhaust microwave radiation rotation heating lactic acid pre-expansion chain processed, after dehydration, add nanometer bi-metal catalyst in the lactic acid, through routine heating or heat-conduction medium negative pressure convection current exhaust microwave radiation rotation heating chain extension precondensation, the precondensation product adds the nanometer single-metal reforming catalyst and adds thermal polycondensation or polymerization gets poly(lactic acid) through the rotation of heat-conduction medium negative pressure convection current exhaust microwave radiation.
4, the manufacture method of biodegradated polymer materal-poly(lactic acid) according to claim 1 and 2, it is characterized in that described direct condensation: add chainextender and nanometer combination binary catalyst in the lactic acid, through routine heating or the polycondensation of heat-conduction medium negative pressure convection current exhaust microwave radiation rotation heating lactic acid continuously dehydrating chain extension, polycondensation product adds nanometer combination binary catalyst and adds thermal polycondensation or polymerization gets poly(lactic acid) through the rotation of heat-conduction medium negative pressure convection current exhaust microwave radiation.
5, the manufacture method of biodegradated polymer materal-poly(lactic acid) according to claim 1 and 2, it is characterized in that described ring-opening polymerization: add chainextender and nanometer single-metal reforming catalyst in the lactic acid, become oligopolymer through routine heating decompression or the polycondensation of heat-conduction medium negative pressure convection current exhaust microwave radiation rotation heating normal pressure dehydration chain extension, oligopolymer add nanometer bi-metal catalyst through routine heating decompression or the cracking of heat-conduction medium negative pressure convection current exhaust microwave radiation rotation heating constant-pressure and high-temperature distill crude lactide, crude lactide gets rac-Lactide from crystallization purifying, and rac-Lactide adds the nanometer single-metal reforming catalyst and makes poly(lactic acid) through heat-conduction medium microwave radiation rotation heating polymerization under atmospheric pressure.
6, the manufacture method of biodegradated polymer materal-poly(lactic acid) according to claim 1 and 2 is characterized in that can adding metal ion purifying agent MD1024 when adding nm-class catalyst.
7, the manufacture method of biodegradated polymer materal-poly(lactic acid) according to claim 1 is characterized in that described chainextender is: vulcabond or tetramethylolmethane or dicarboxylic anhydride or sorbyl alcohol or adjacent benzene tetracarboxylic acid or diepoxide class or bisoxazoline class.
8, the manufacture method of biodegradated polymer materal-poly(lactic acid) according to claim 1, it is characterized in that described heat-conduction medium negative pressure convection current exhaust microwave heating, be to utilize inner heating characteristics of microwave and vacuum fan to form the negative pressure convection current, make the inside and outside pressure gradient that produces of filter cake discharge the purpose that the steam moisture content that dewaters in the lactic acid reaches the acceleration acid by dehydrating lactic, the exhausting system of dehydration equipment can be walked moisture content by convective zone on the one hand, makes dewatering system form the dissipation that negative pressure prevents the sour gas that lactic acid at high temperature produces on the other hand.
9, the manufacture method of biodegradated polymer materal-poly(lactic acid) according to claim 1 is characterized in that described heat-conduction medium can select silicon carbide Sic or dissipative type material for use.
10, the manufacture method of biodegradated polymer materal-poly(lactic acid) according to claim 9; it is characterized in that described heat-conduction medium silicon carbide powder or powder; after directly place mat mixes at reactor bottom or by 3 to 1 ratio and TTZF type tackiness agent; smear or embed below effective loading of the glass reactor of anti-burning of manufacturing or ceramic reactor, between the ectonexine of reactor outside and bottom or outside and bottom.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410013681 CN1280332C (en) | 2004-04-12 | 2004-04-12 | Manufacturing method of biodegradable high polymer material-polylactic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410013681 CN1280332C (en) | 2004-04-12 | 2004-04-12 | Manufacturing method of biodegradable high polymer material-polylactic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1651479A true CN1651479A (en) | 2005-08-10 |
| CN1280332C CN1280332C (en) | 2006-10-18 |
Family
ID=34867825
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410013681 Expired - Fee Related CN1280332C (en) | 2004-04-12 | 2004-04-12 | Manufacturing method of biodegradable high polymer material-polylactic acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1280332C (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT506040B1 (en) * | 2007-11-14 | 2012-03-15 | Jungbunzlauer Austria Ag | PARTICULATE CATALYST AND CATALYST / STABILIZER SYSTEMS FOR THE PRODUCTION OF HIGH-MOLECULAR HOMO- AND COPOLYESTERS OF L-, D- OR D, L-MILKYLIC ACID |
| CN101608350B (en) * | 2008-06-20 | 2012-07-25 | 东丽纤维研究所（中国）有限公司 | Polylactic fiber with high hydrolytic resistance |
| US8431678B2 (en) | 2007-11-14 | 2013-04-30 | Jungbunzlauer Austria Ag | Method for producing cyclic diesters of L-, D- and D,L-lactic acid |
| CN103072958A (en) * | 2013-01-31 | 2013-05-01 | 哈尔滨工业大学 | Preparation method of manganese-base anti-perovskite nitride |
| EP2905297A1 (en) * | 2014-02-10 | 2015-08-12 | Samsung Electronics Co., Ltd | Polylactic acid preparation method, polylactic acid resin prepared using the method, resin composition comprising the polylactic acid resin, and catalyst system for preparing polylactic acid |
| CN113583404A (en) * | 2021-07-07 | 2021-11-02 | 安徽联科水基材料科技有限公司 | Anti-dripping flame-retardant polylactic acid composite material and preparation method thereof |
| CN113698583A (en) * | 2021-09-08 | 2021-11-26 | 刘青 | Method for directly synthesizing high molecular weight polylactic acid |
| WO2023282864A1 (en) * | 2021-07-09 | 2023-01-12 | Md Poli̇mer Gida Sanayi̇ Ti̇caret Li̇mi̇ted Şi̇rketi̇ | Synthesis of poly(lactic acid) catalyzed by nanoparticle metal |
-
2004
- 2004-04-12 CN CN 200410013681 patent/CN1280332C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT506040B1 (en) * | 2007-11-14 | 2012-03-15 | Jungbunzlauer Austria Ag | PARTICULATE CATALYST AND CATALYST / STABILIZER SYSTEMS FOR THE PRODUCTION OF HIGH-MOLECULAR HOMO- AND COPOLYESTERS OF L-, D- OR D, L-MILKYLIC ACID |
| US8431678B2 (en) | 2007-11-14 | 2013-04-30 | Jungbunzlauer Austria Ag | Method for producing cyclic diesters of L-, D- and D,L-lactic acid |
| CN101608350B (en) * | 2008-06-20 | 2012-07-25 | 东丽纤维研究所（中国）有限公司 | Polylactic fiber with high hydrolytic resistance |
| CN103072958A (en) * | 2013-01-31 | 2013-05-01 | 哈尔滨工业大学 | Preparation method of manganese-base anti-perovskite nitride |
| EP2905297A1 (en) * | 2014-02-10 | 2015-08-12 | Samsung Electronics Co., Ltd | Polylactic acid preparation method, polylactic acid resin prepared using the method, resin composition comprising the polylactic acid resin, and catalyst system for preparing polylactic acid |
| KR20150094096A (en) * | 2014-02-10 | 2015-08-19 | 삼성전자주식회사 | Preparation method of polylactic acid, polylactic acid resin prepared therefrom, resin composition comprising the resin, and catalyst system for preparing polylactic acid |
| US9234075B2 (en) | 2014-02-10 | 2016-01-12 | Samsung Electronics Co., Ltd. | Polylactic acid preparation method, polylactic acid resin prepared using the method, resin composition comprising the polylactic acid resin, and catalyst system for preparing polylactic acid |
| CN113583404A (en) * | 2021-07-07 | 2021-11-02 | 安徽联科水基材料科技有限公司 | Anti-dripping flame-retardant polylactic acid composite material and preparation method thereof |
| WO2023282864A1 (en) * | 2021-07-09 | 2023-01-12 | Md Poli̇mer Gida Sanayi̇ Ti̇caret Li̇mi̇ted Şi̇rketi̇ | Synthesis of poly(lactic acid) catalyzed by nanoparticle metal |
| CN113698583A (en) * | 2021-09-08 | 2021-11-26 | 刘青 | Method for directly synthesizing high molecular weight polylactic acid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1280332C (en) | 2006-10-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1280332C (en) | Manufacturing method of biodegradable high polymer material-polylactic acid | |
| CN1061222A (en) | Produce rac-Lactide by dehydration of aqueous lactic acid feed | |
| CN113559921B (en) | Metal loaded mesoporous carbon-ZSM-5 molecular sieve shell-core catalyst and preparation and application methods thereof | |
| CN107469802A (en) | It is a kind of to be used to produce catalyst of rich aromatic hydrocarbons bio-fuel-oil and preparation method thereof | |
| CN113117748A (en) | Bicyclic guanidine salt eutectic solvent catalyst and preparation method and application thereof | |
| CN110452123B (en) | Synthesis method for constructing C-C, C-N, C-S bond in one step | |
| CN113603584B (en) | Method for photo-thermal degradation of polyester | |
| CN109400856B (en) | Method for catalytically synthesizing polytrimethylene terephthalate with high intrinsic viscosity and good hue by adopting metal composite catalyst | |
| CN1923954A (en) | Catalytic cracking coking mother granule | |
| CN1850875A (en) | Phenolic resin and its production process | |
| CN86107833A (en) | Zinc oxide catalytic agent for synthesizing of acetic acid ethylene | |
| CN1140563C (en) | Method for producing polybutylene terephthalate | |
| CN116422337A (en) | Catalyst for preparing hydrogen by reforming methanol-water driven by microwave and preparation method thereof | |
| CN1120049C (en) | Supported type heteropolya cid catalyst in synthesis of ethylene glycol series monoethers acetate | |
| CN102212185A (en) | Method for preparing high-melting-point polylactic acid composite material | |
| CN1100614C (en) | Solid catalyst for synthesizing glycol monoether acetate | |
| CN110052259B (en) | Preparation and application of silicon dioxide coating type monolithic catalyst | |
| CN110817840B (en) | Method for carbonizing polyolefin | |
| CN1168534C (en) | Prepn of catalyst for tetramethylbenzene isomerization to prepare durene | |
| CN1284778C (en) | Method for preparing lactide by microwave radiation | |
| CN1053598C (en) | Zirconium oxide catalyst used in glycol series monoether acetate synthesis | |
| CN111269254B (en) | Microwave synthesis method of 1, 3-bis [2- (3, 4-epoxycyclohexyl) ethyl ] tetramethyldisiloxane | |
| CN1640910A (en) | Unsaturated polyester synthesizing method | |
| CN1228290C (en) | Method for preapring benzo cyclonbutene from benzo cyclopent sulfone high-temperature catalytic cracking | |
| CN115197174B (en) | Binaphthol-based epoxy resin monomer, preparation method thereof and application thereof in preparation of all-bio-based epoxy resin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |